Compositions and methods of improving the quality of human hair with stable methylol compounds

ABSTRACT

Methylol compounds which do not liberate free formol and are therefore suitable for cosmetic use, compositions including said compounds, and methods of using said compositions to improve the cosmetic properties of human hair. Exemplary methylol compounds are the methylolureas, and they may be prevented from liberating harmful amounts of free formol by including therein an electrophile group selected from among those responding to the formula:   IN WHICH X is selected from the group consisting of an oxygen atom and a sulfur atom and R&#39;&#39;&#39;&#39; is selected from the group consisting of a hydrogen atom, an alkyl radical and an NH2 group.

United States atent 1 Kalopissis et al.

[ Nov. 20, 1973 COMPOSITIONS AND METHODS OF IMPROVING THE QUALITY OFHUMAN HAIR WITH STABLE METHYLOL COMPOUNDS [75] Inventors: GregoireKalopissis, Paris; Jean Louis Abegg, Le Perreus; Henry DeBeaulie;Giuliana Ghilardi, both of Paris, all of France [73] Assignee: SocieteAnonyme Dite: LOreal [22] Filed: Mar. 5, 1971 [21] Appl. No.: 121,515

Related US. Application Data [63] Continuation of Ser. No. 631,156,April 17, 1967,

abandoned.

[52] US. Cl. 132/7, 8/127.51, 8/127.6, 424/DIG. 1, 424/47, 424/70,424/71 [51] Int. Cl. A45d 7/04, A45d 7/06 [58] Field of Search 424/76,71, 47; 132/7 [56] References Cited UNITED STATES PATENTS 1,871,0878/1932 Schneevoigt et a1 117/139.4 X 2,235,141 3/1941 Dreyfus et a1.91/70 2,254,001 8/1941 Conaway 91/70 2,342,785 2/1944 Bock et a1 117/1612,836,185 5/1958 Hervey 424/72 2,836,543 5/1958 Watson 424/72 3,116,967l/1964 Goldstein et a1 8/1 15.6

9/1964 Habicht et al. 424/70 10/1967 Joos 424/70 X OTHER PUBLICATIONSSagarin, Cosmetic Science and Technology, Interscience Pub., lnc., N.Y.,p. 609, (1957) Wells & Lubowe, Cosmetics and the Skin, Reinhold Pub.,Corp., N.Y., p. 475, (1964) Primary ExaminerAlbert T. Meyers AssistantExaminerFrederick E. Waddell Attorney-Cushman, Darby & Cushman [5 7]ABSTRACT Methylol compounds which do not liberate free formol and aretherefore suitable for cosmetic use, compositions including saidcompounds, and methods of using said compositions to improve thecosmetic properties of human hair. Exemplary methylol compounds are themethylolureas, and they may be prevented from liberating harmful amountsof free formol by including therein an electrophile group selected fromamong those responding to the formula:

from the group consisting of a hydrogen atom, an alkyl radical and anNI-I group.

23 Claims, N0 Drawings COMPOSITIONS AND METHODS OF IMPROVING THE QUALITYOF HUMAN HAIR WITH STABLE METHYLOL COMPOUNDS This is a continuation ofUS. Pat. application Ser. No. 631,156, filed Apr. 17, 1967.

This invention relates to a cosmetic composition for improving thecosmetic properties of human hair which has become degraded, and therebyconfer on the hair the strength and appearance which it possessed beforedegradation.

It is well known that hair undergoes more or less substantialdegradation when exposed to atmospheric agents such as sea water and thesun, or when subjected to chemical treatments such as permanent wavesand blcaches.

The effects of such degradations may be to a large extent eliminated byusing the compositions according to the invention.

It has already been suggested that the strength and elasticity of thehair be improved by treating it with compositions which containsolutions of dimethylolurea and dimethylolthiourea so as to obtain thedesired result by the polymerization or condensation of these activecompounds on the keratine.

This method cannot, however, be applied in practice because, as is wellknown, compositions having a dimethylolurea or a dimethylolthiourea baseare relatively unstable and soon release substantial quantities of freeformol. As the cumulative effect of this liberation of formol duringstorage of the composition and during its application to the hair, thecomposition contains a relatively high concentration of free formol,which is disadvantageous because the free formol is in contact with thescalp.

Since formol is known to be a toxic substance which cannot be applied tothe scalp in substantial quantities without producing undesirableeffects, legislation in force in most countries prohibits theapplication to the skin or scalp of compositions containing more than avery weak concentration of formol, usually of the order of 0.2 percent.

For this reason, the above-mentioned compositions, based ondimethylolurea and dimethylolthiourea, cannot be used in practice,since, when applied to the head, they contain concentrations of formolsubstantially greater than those permitted by law.

Moreover, dimethylolurea and dimethylolthiourea, which are powders whenin the pure state, are difiicult to dissolve in water, which makes itinconvenient to prepare compositions containing them at the moment ofuse.

These dimethylolurea and dimethylolthiourea powders are also difficultto keep, even while taking the customary precautions relative to theirstorage, so that the degradation which occurs during storage increasesthe difficulties encountered in dissolving them in water.

The present invention relates to compositions for strengthening the hairwhich contain methylol compounds having characteristics to some extentanalogous to those of dimethylolurea and dimethylolthiourea. However,due to the choice of the particular active compounds which they contain,the compositions according to the invention have the advantage that theyliberate only small quantities of formol, so that they conform tolegislative requirements and are safe to use.

Moreover, the compositions according to the invention have certainadvantages over those previously described which will be hereinafter setforth.

Several interrelated approaches to the problem of preparing suchcompositions have been discovered. Each approach has lead to thedevelopment of a plurality of satisfactory compounds, and in many casesone or more of the compounds developed by research along one line ofapproach has also been found when proceeding along another line ofapproach.

In a first embodiment of the invention there is provided a new articleof manufacture which consists of a cosmetic composition characterized bythe fact that it contains, in a suitable cosmetic vehicle, at least onepartially polymerizable compound which forms bonds with the keratin ofthe hair, and which is of to the following formula:

lt-N-CIIzOII in which:

R represents a substituent which is sufiiciently electrophile to preventthe immediate release of a formol molecule,

R represents a hydrogen atom, an alkyl radical, a hydroxyalkyl radical,or a substituent of the same type as R, and

R and R may form part of a nitrogenous heterocyclic ring which may havea methylol group attached to the nitrogen.

In a particular embodiment of the invention the substituent R of theformula (I) is a group of the formula:

in which: 7

X represents an oxygen atom or a sulfur atom,

R" represents a hydrogen atom, an alkyl radical, or an alkoxy radical,and these radicals may have an amidic or carbamic group having amethylol group attached to the nitrogen.

X represents an NH radical, and

R represents an -NH-R" group, in which R is a hydrogen atom, ahydroxymethyl radical, or an C E N radical.

In another embodiment of the invention the substituent R of the formula(I) is a group of the formula:

in which R represents an alkyl group, and aryl group, or an alkylarylgroup.

Among the methylol compounds defined above which may be selected forintroduction into the composition according to the invention are thefollowing, but this is by no means exhaustive:

monomethylol ethyl carbamate having the formula:

dimethylol methylene ethyl bis-carbamate having the formula:

HgOH H OH 5 dimethylol succinamide having the formula:

non c-Nir-j(H2)zc-N1I-cn 0n W monomethylol guanidine carbonate havingthe formula: l

[NII;-(]?NIIJ+:|CO3-[NII3+%FNHCH;OH]

Il NII I N-methylol paratoluene sulfamide having the formula:

CH3SO;NHCH;OH

- dimethylol adipamide having the formula:

1IOII CNHC(CH;)4CNHCHzO1I 3O N ,N '-dimethy]ol-( Z-methyLZ-propyl)-propylene bis-carbamade having the formula:

i H0H2CNHo0CH -c-O1I op-NHcH30H monomethylol dimethylhydantoin havingthe formula:

C-CO

113C N-CHOII NH--CO monomethylol ethyleneurea having the formula:

CHzOH CH2N \CO H,Nfi

monomethylolethylene thiourea having the formula:

/CH20H OH N 5 CH2NH dimethylol ethylene thiourea having the formula:

The composition according to this embodiment of the invention mayadvantageously contain 0.1 to 10 percent and preferably from I to 3percent by weight of the methylol compounds.

In a preferred form of this embodiment of the invention the compositionalso contains an acid catalyst, which may be an acid or an acid mineralor organic salt suitable for use in cosmetic products.

The composition according to this embodiment of the invention mayconsist of an aqueous or hydroalcoholic solution of methylol compounds.It may also take the form of a gel or cream, or aerosol.

The composition according to this embodiment of the invention may alsocontain other ingredients conventionally used in cosmetics, such asperfumes, dyes, surface-active agents, swelling agents, resins, etc.

The compositions according to this embodiment of the invention offer theadvantage of having satisfactory stability and of releasing free formolonly in quantities so small that they are not injurious when thecomposition is applied to the hair.

Moreover, the compositions according to this embodiment of the inventionhave the advantage of yielding better cosmetic results with respect tothe appearance and springiness of the hair than the abovementionedcompositions based on dimethylolurea and dimethylolthiorea.

It appears that this results from a slower speed of polymerization and,doubtless, from a different polymerization process, in which the activecompounds of the compositions according to the invention seem to have amore marked tendency to form bonds with the keratin than to undergocondensation or polymerization as strictly defined.

Moreover, the compositions according to the embodiment of the inventionmay be easily packaged in the form of a powder which may then bedissolved in an aqueous or hydroalcoholic liquid medium. This is madeeasy by the fact that the methylol compounds used in the invention havethe great advantage of dissolving much more easily in aqueous media thando dimethylolurea or dimethylolthiourea, which have a tendency to remainin suspension, which is incompatible with their use for cosmeticpurposes.

Finally, the methylol compounds used in accordance with the inventionhave the advantage of being generally chemical compositions which arerelatively easy to prepare in the pure state, which makes it possible toinsure a constant quality in production and reproducible results.

These advantages are in addition to the fact that, as has already beenindicated, the compositions according to this embodiment of theinvention have no marked tendencies to liberate free formol.

The present invention also relates to a method of treating the haircharacterized by the fact that the hair is impregnated by one of thecompositions hereinbefore described, and is then dried, preferably byapplying external heat.

In a first method of carrying out the foregoing invention the cosmeticcomposition does not itself contain the acid catalyst necessary topolymerize the methylol compounds in the keratinic fiber, this catalystbeing applied independently to the hair before or after the compositionaccording to the invention.

In another method of carrying out the invention, the cosmeticcomposition, with the polymerization catalyst already incorporatedthereinto is applied directly to the air, which is then dried in themanner which has just been described.

The cosmetic characteristics of hair which have been degraded oraltered, by bleaching for example, may thus be efficaciously restored.

In order that the foregoing invention may be better understood, severalexemplary methods of carrying out the invention will now be described,purely by way of illustration and example:

EXAMPLE A1 The first step of a permanent wave is carried out in aconventional manner, using the following composition:

Thioglycolic acid 8 g Monoethanolamine q.s.p. pH 9.5 Monomethyloldimethyl hydantoin 6 g Water q.s.p. 100

The hair is impregnated with this solution, the impregnated locks ofhair are rolled up on curlers of a normal diameter, the hair is againsaturated with the solution and left for 15 minutes under a plastic capat the ambient temperature. The hair is then rinsed and an aqueoussolution of hydrogen peroxide at 6 volumes, the pH of which has beenadjusted to 1.5 by the addition of phosphoric acid, is applied.

The hair is then placed under a hood and dried in a conventional manner.

EXAMPLE A2 After having bleached the hair in a conventional manner, thefollowing composition is applied:

Monomethylol ethylene urea 4 g Monosodium phosphate 0.3 g Water q.s.p.100 cc The hair is then set in a conventional manner and excellentresults are obtained, especially with respect to its springiness andholding power.

EXAMPLE A3 A solution having the following composition is applied, as inExample A2 to hair which has first been bleached and washed:

Monmethylol ethylene thiourea 5 g Phosphoric acid q.s.p. pH 2.5 Waterq.s.p. 100 cc The hair is left under a hood for about minutes,remoistened, and permanently waved in a conventional manner. The hair isthen found to be in excellent condition, particularly with respect toits tips, and both the appearance and life of the permanent wave areincreased.

EXAMPLE A4 Bleached hair is first shampooed with a cationic acidshampoo. It is then rinsed and carefully dried, after which thefollowing solution is applied:

Dimethylol ethylene thiourea 4 g Polyvinylpyrrolidone vinyl acetatecopolymer 2 g Ethyl alcohol 25 cc Perfume 0.1 g Water, q.s.p. cc

The hair is then dried in a conventional manner for 30 minutes at 50 C.

EXAMPLE A5 A solution having the following composition is applied tohair which has first been given a conventional permanent wave, and thenrinsed and dried:

Monomethylol ethylene thiourea 8 g Monomethylol ethyl carbamate 2 g 10%lactic acid 3 cc Water 97 cc The entire head of hair is then set in aconventional manner.

EXAMPLE A6 A solution having the following composition is applied tohair which has been bleached, just before setting it:

Dimethylol methylene ethyl bis-carbamate 0.5 g Citric acid q.s.p. pH=3.5 Water q.s.p. 100 cc EXAMPLE A 7 Under the same conditions as inExample A6, a solution having the following composition is applied tothe EXAMPLE A8 A solution having the following composition is applied tohair which has previously been bleached:

N,N'-dimethylol (2-methyl-2-propyl)-pnopylene bis-carbamate l gDimethylol ethylene thiourea 0.3 g 10% phosphoric acid q.s.p. 1.5 Waterq.s.p. 100 cc The hair is then set in a conventional manner.

EXAMPLE A9 A gel having the following composition is applied, beforesetting it in a conventional manner to hair which has first beenbleached, and then washed and rinsed in a citric acid solution having apH of 3.5:

Oleic alcohol 10 moles O.E. (Bn'j 96) 23 g Parafim oil 22 g Dimethyloladipamide 2 g Perfiune 0.2 3 Water 55 g EXAMPLE A10 A gel having thefollowing composition is applied to hair just before setting it, underthe same conditions as in Example A6:

Oleic acid 10 moles 015. 27 g Paraffin oil 23 g Monomethylol ethyleneurea 0.5 g Pure acetic acid qsp pH 3.5 Water 50 cc EXAMPLE Al 1 10 cc ofa phosphoric acid solution having a pH value of 2 are applied to hairwhich has previously been given a permanent wave, rinsed, and dried. Acream having the following composition is then applied:

Lanette AO wax Oleic alcohol Cetyl trimethylammonium bromideMonomethylol ethyl carbamate Water 8 The hair is then set in aconventional manner.

EXAMPLE A12 A solution having the following composition is applied to ahead of hair under the same conditions as in Example A6:

Monomethylol paratoluene sulfarnide l g 10% lactic acid l cc Ethylalcohol 30 cc Perfume 0.1 g Water 99 cc EXAMPLE A13 A solution havingthe following composition is ap plied to a head of hair under the sameconditions as in Example A6:

Monomethyl guanidine carbonate 3 g Compound having the formula:

Cw i: z a

CH -CON-(CH2)3-N 0.2 g.

RNH-CH-COONa 11 i "I (R =Copraj Sulfuric acid, q.s.p. pH L5 Water q.s.p.100

By using the compositions according to the invention in the waysdescribed in the examples set forth above the hair is made brighter andspringier.

Moreover, and especially when the hair has been bleached, the hairbecomes more pleasant to touch and easier to comb.

Waves which have been made according to the invention also have greaterholding power.

Finally, no undesirable cumulative effects have been found to resultfrom repeating treatments in accordance with the invention as often asnecessary for normal hair care.

In the second approach to the problem, it has been found particularlyeffective to employ a cosmetic composition characterized by the factthat it comprises in combination at least one at least partialiypolymerizable composition which will form bonds with the keratin of thehair and comprising at least one group of the formula in which Rrepresents a hydrogen atom, a lower alkyl radical, a hydroxymethylradical, or an alkoxymethyl radical and R represents a hydrogen atom ora lower alkyl radical; the nitrogen atom of the group being attached toa group which is sufficiently electrophile to insure the chemicalstability of the group, that is to say, to avoid any immediate releaseof a formol molecule together with at least one nitrogen derivativecomprising at least one group of the following formula in which Xrepresents an oxygen atom, a sulfur atom, or an NH radical, and in whichboth X and the carbon atom may form part of a heterocyclic ring In thecompositions according to the invention, the number of NH groupssupplied by the nitrogen derivatives is between 0.1 and 1.0 times andpreferably between 0.1 and 0.3 times the number of methylol groupssupplied to the composition by the methylol com pounds.

Among the methylol compounds which may be used in carrying out theinvention are:

Monomethylol dimethylhydantoin Monomethylol ethylene urea Dimethylolethylene thiourea Monomethylol ethyl carbarnate Dimethylol ethyleneethyl bis-carbamate Dimethylol succinamide Monomethylolethylene thiourea(The formula for each of the above compounds has already been givenduring the description of the first embodiment.

Dimethylolthiourea of the formula:

- Dimethylolurea of the formula:

It should be noted that these two prior art compounds are suggested onlyfor use in conjunction with the nitrogen compounds disclosed in thisembodiment of the invention. It is not recommended that they be used asthe sole active ingredient as the compounds listed in connection withthe first embodiment may be used.

- Monomethylolurea of the formula:

Monomethylolthiourea of the formula:

CHZOH +11 /C Homo-NH N NHCHOH M Monomethyloldicyandiamlde of theformula:

NECNHC-NHCHZOH N U: h

15 Bismethoxymethylurea of the formula:

oHaooH -NH-p-NHcHoHa .mummwa at. 20

- Monomethylol guanidine of the formula:

H N-C-NH-CHzOH I II N,N-dimethylol (2-methyl-2-propyl) propylenebiscarbamate of the formula:

(IJHS 0 HOH2CNH-(|JOCHZ(FCH2OFNHOH2OH 3 when." V .WFiEL, 7* Dimethyloladipamide of the formula:

' HOII CNII-C(CIIz)4CNHCH OII N,N-diethyl N-methylolurea of the formula:40

N-C-NH-CHzOH N,N-dimethylol ethyleneurea of the fornula:

/omolt CH2N\ /C=O CHz-N\ w m P3 WHWHM Dimethylol ethyl carbamate of theformula:

CH2OH EtO-C-N @9592. an mt- Tetramethylol acetylenediurea of theformula:

HOHzC-N-CH-N-CHzOH 0:0 0:0

Among the nitrogen compounds which may be used in carrying out theinvention are: Urea of the formula:

Melamine of the formula:

Dicyandiamide of the formula:

NEG-NH-C-NHz N,N diethyl urea of the formula:

Ethylene urea of the formula: V

-- lsopropyl carbamate of the formula:

- Dimethyl hydantoin of the formula:

NI l

Nll-(JO Ethylene thiourea of theformula:

Guanidine carbonate of the formula:

Succinamide of the formula:-

in a preferred form of this second embodiment of the invention, thecomposition comprises a nitrogen derivative mixed with the correspondingmethylol derivative, that is to say, one obtained by reacting formolwith said nitrogen derivative.

in accordance with the preferred form of this second embodiment of theinvention the concentration of the methylol derivatives may vary withinbroad limits, but remains generally between 0.5 and 12 percent. Thisconcentration is dependent in part on the solubility of thesederivatives in water and in part on the state of the hair to be treated.Bleached hair is preferably treated with lower concentrations than hairwhich has not been bleached.

The new cosmetic composition may take the form of an aqueous orhydro-alcoholic solution and may serve as a setting lotion in which caseit may contain any of the cosmetic additives conventionally included insuch lotions.

The new cosmetic composition may also be used as a neutralizing lotionfor permanent waves, in which case it will also comprise at least oneoxidizing agent and the additives conventional in such lotions.

The composition may also take the form of a gel, cream, or aerosol, andcontain surface-active agents, swelling agents, dyes or perfumes.

Another object of this second embodiment of the invention is to providea method of storing the said composition, characterized by the fact thatthe methylol products are in the solid state and the nitrogenderivatives are in a solution which also contains an acid.

The methylol products may then be dissolved, at the time of use on thehair, in the acid solution which already contains the nitrogenderivative.

ln accordance with the embodiment of the invention the methylolcompounds may also be mixed with the nitrogen derivatives and a separateacid catalyst prepared, which may be in solution, or in solid form. Thiscatalyst may be mixed with the solution containing the methylolcompounds and the nitrogen derivatives at the time the composition is tobe used on the hair.

The cosmetic compositions according to this embodiment of the inventionhave the advantage of liberating less formol than thosemethylol-containing compositions heretofore known, such a dimethylolureaand dimethylolthiourea. It has been established that the addition of thenitrogen compounds according to the invention will in general reduce bymore than 50 percent the amount of free formal present at the time thecosmetic compositions containing the methylol derivatives are used.

Moreover, the addition of nitrogen derivatives to the cosmeticcompositions containing the methylol compounds makes it possible tostore these compositions more easily in solution, since the release offormol, which normally takes place under these conditions, is preventedby the presence of the nitrogen compounds.

A further object of this second embodiment of the isnvention is toprovide a method of treating hair, which method is characterized by thefact that the hair is impregnated with a cosmetic solution such as thathereinafter described, that an acid polymerization catalyst is thenadded if the solution does not already include it, and the hair is driedby applying external heat, after having been rinsed, if desired.

This brings about a group of reactions within the keratinic fibers ofthe hair which tend to create bonds between the fibers and to strengthenthe inner parts of the fibers themselves by polymerization of themethylol compounds.

in order that the invention may be better understood, several methods ofcarrying out the invention will now be described, purely by way ofillustration:

EXAMPLE Bl After having first bleached and dyed the hair in aconventional manner, a solution having the following composition isapplied:

Dimethylolurea 2 g Urea 1,5 g Citric acid 0.2 cm Water q.s.p. cm

EXAMPLE B2 At the moment at which it is to be used a solution having thefollowing composition is prepared:

Monomethylolurea 9 g Urea 6 g Acetic acid q.s.p. pH 3 Water q.s.p. 100cc After washing and drying the hair, this solution is applied in aconventional manner as a setting lotion and the hair is dried for 30minutes at about 50 C. The result is a wave which is springy ab initioand the hair holds the wave well over the course of time, even whenexposed to humid air.

EXAMPLE B3 After having bleached the hair in a conventional manner, asolution having the following composition is applied:

Dimethylolurea [.2 g Ethyleneurea 0.5 g Citric acid q.s.p. pH 3 Waterq.s.p. 100 cc The hair is then set in a conventional manner andexcellent results are obtained with respect to the springiness of thehair and the durability of the wave.

EXAMPLE B4 Under the same conditions as in Example B3 the followingsolution is applied:

Dimethylolthiourea 2 g Urea 0.9 g 10% lactic acid q.s.p. pH 1.5 Waterq.s.p. 100 cc Equally good results are obtained.

EXAMPLE B The following solution is prepared just before use:

Trimethylolmelamine 4.2 g Ethyleneurea 1.6 g Acetic acid q.s.p. pH 3Water q.s.p. 100 cc This is applied in a conventional manner as asetting lotion to hair which has first been given a permanent wave. Thehair is then dried for 40 minutes at 50 C. The hair which has been thustreated is found to be springy ab initio and holds the wave well over asubstantial period of time.

EXAMPLE B6 A solution having the following composition is applied tohair which has first been bleached and dyed:

Monomethylol dicyandiamide Urea Cetyltrimethylammonium bromidephosphoric acid q.s.p.

Water q.s.p.

The hair is then set in a conventional manner, and dried under a dryinghood at a temperature of 4550 C. It is found that hair treated in thismanner is brighter, combs easily and is more agreeable to the touch thanhair which has been bleached, dyed, and set under identical conditionsexcept that the process according to the invention was not used.

EXAMPLE B7 Under the same conditions as in Example B6, a solution havingthe following composition is applied to the hair:

Equally good results are obtained.

EXAMPLE B8 Under the same conditions as in Example B3, a solution havingthe following composition is applied to the hair:

Dimethylolethyleneurea 2.9 g Urea .07 g Ext. violet DC No. 2 (CJ. acidviolet No. 43) 0.004 g Sulfuric acid q.s.p. pH 2 Water q.s.p. 100 ccEqually good results are obtained with respect to the quality of thehair and the durability of the wave.

All of the compositions according to this second embodiment of theinvention which have been hereinbefore described are clearly more stablethan compositions which do not include the nitro derivatives which areadded by the invention. In particular, experience has shown that whenthe compositions which have been described are kept at a temperature of50 C. for 30 minutes, they contain at least 2 to 4 times less freeformol than the same compositions when they do not contain nitroderivatives.

In generaly, the addition of nitro compounds according to thisembodiment of the invention greatly facilitates the storing and theconditions of application of the methylol composition in that they makeit possible to substantially reduce the concentration of free formol,which concentration is thereby reduced within perfectly acceptablelimits.

It will be noted that monomethylol dicyandiamide is among the methylolcompounds suggested for use according to the second embodiment of thisinvention in combination with a nitro compound.

In accordance with a third embodiment of the invention it has been foundthat not only monomethyloldicyandiamide but other compounds of theformula:

in which R represents either a hydrogen atom or an alkyl remainder, maybe used without the nitro compound. Methoxymethyloldicyandiamide, forexample, is suitalbe, and it is within the scope of the invention toemploy ethers thereof corresponding to the above formula.

A particular disadvantage of the dimethylolurea and dimethylolthioureasuggested by the prior art stems from the fact that since they aresubstantially insoluble in water they have a cumulative effect so thatwhen repeatedly applied they render the hair hard and brittle. Thecompositions according to this third embodiment of the invention,however, may be removed by simply washing the hair so as to avoid anyundesirable cumulative effect.

The compounds of the foregoing formula are also sufficiently stable toprevent the release of more than a small quantity of formol, so thatthey may be safely employed in cosmetic compositions, and impart animproved brightness, fluffyness, and feel to the hair.

Monomethyloldicyandiamide keeps well when in powder form, and is easy todissolve at the moment of use. It is also stable in aqueous solution, sothat a 20 percent aqueous solution of monomethyloldicyandiamide may bestored for substantial lengths of time and then diluted as required atthe moment of use, with an acid solution which serves as a catalyst, forexample.

The ethers of monomethylolcyandiamide, and particularly methoxymethyldicyandiamide may also be used but are less water-soluble thanmonomethylolcyandiamide itself. These ethers may, however, be renderedsufficiently soluble to permit their use for cosmetic purposes byemploying water which has been heated to about 50 C. Solutions ofmonomethyloldicyandiamide ethers having a concentration of severalpercent may be obtained in this manner, and the ethers do notreprecipitate out when the solution is cooled to room temperature.

The solubility of these ethers may also be increased without any adverseeffect on their cosmetic properties, by proceeding in the followingmanner:

The alkoxymethylol derivative of the product is reacted with not morethan 0.5 mol of hydrochloric acid per mol of thealkoxymethyldicyandiamide and the produce isolated therefrom is used inpowder form. Under these circumstances the product is sufficientlysoluble in either water or alcohol to make it fully practical to preparesolutions having a concentration of the order of 2 percent.

Three representative solubilizing methods will now be described Method I100 g of methoxymethyldicyandiamide in suspension in 100 cc of absoluteethyl alcohol are added to 25 cc of 12 N hydrochloric acid. The mixtureis then heated to 40 C and agitated until dissolution. The result is a20 percent ethanolic solution of the methoxymethylol product. Thissolution may be directly used after dilution in acidulated water at themoment of use, as will be hereinafter indicated.

Method ll 1 14 g Ci moi/g) of monomethyloldicyandiamide are dissolved ina liter of methyl alcohol in the presence of cc (0.06 mols) of 12 Nhydrochloric acid. The mixture is brought to 30 C until dissolution. Thecorresponding methyl ether is obtained. The excess methanol is thendriven off by heating under vacuum.

The result is a powder which can be used either as is, after dissolutionin water at the moment of use, or dissolved in a suitable alcohol, suchas ethanol, and used in the form of this solution, as will behereinafter set forth.

Method III 114 g 1 mol/g) of monomethyloldicyandiamide are dissolved in700 cc of ethanol in the presence of 35 cc of hydrochloric 12 N acid.The mixture is heated at 30 C until dissolution. The result is an ethylalcohol solution containing 20 percent of a derivative of the ethylether of monomethyloldicyandiamide.

This ethyl solution may be used in accordance with the invention in thepreparation of cosmetic compositions.

Such compositions may advantageously contain from 0.2 to percent andpreferably from I to 4 percent by weight of the active compoundsdescribed above.

These compositions may take the form of aqueous or hydroalcoholicsolutions, gels, creams, emulsions or aerosols.

They may of course contain any additives conventionally used incosmetics such as perfume, dyes, surface-active agents, swelling agents,etc.

This third embodiment of the invention also includes the new method ofimproving the properties of degraded hair, which method is essentiallycharacterized by the fact that a composition such as described above isapplied to the hair with an acid catalyst, that the product is left toact on the hair for from to 40 minutes, for example, while the hair isbeing dried.

In a first method of carrying out this third form of the invention, theacid catalyst is included in the composition before it is applied to thehair.

In a second method the acid catalyst is applied separately to the hair,either before or after the composition according to the invention.

Any substance compatible with cosmetic use, and which permits the pH tobe lowered sufficiently to permit the polymerization or condensation ofthe active products according to the invention may be used as thecatalyst.

It is also possible to use organic acids such as acetic acid, lacticacid, citric acid or even mineral acids and acid salts such asphosphoric acid and sulphuric acid.

The results achieved are particularly impressive when treating hairwhich has been previously bleached or bleached and dyed with anoxydation dye.

In this case the hair may advantageously be treated during the course ofa setting process. The hair becomes brighter, more manageable, easier toarrange, and easier to comb. The hair also becomes harder and fluffier.Furthermore, when the products according to the invention are applied tothe hair they impart thereto an improved holding power, regardless ofwhether the hair has first been bleached or not. Finally, it is foundthat any color imparted by a dye is more marked and the sets are longerlasting.

In order that this third form of the invention may be better understood,several examples thereof will now be given, purely by way ofillustration:

EXAMPLE Cl A solution having the following composition is applied tohair which has been repeatedly bleached:

Monomethyloldicyandiamide l0 g Cetylpyridinium bromide 0.l g Phosphoricacid q.s.p. pH 2.5 Water q.s.p. g

The hair is dried under a hood for about 30 minutes at 45 C and thenpermanently waved in a conventional manner, using a reducing solutioncontaining ammonium thioglycolate.

After this the hair is set in a conventional manner and it is found thathair treated in this manner is very springy, fluffy, bright, and hascosmetic qualities clearly superior to those of hair which has beenpermanently waved, but not treated in accordance with the invention.

EXAMPLE C2 The following composition is applied to hair which has firstbeen bleached, rinsed and dried:

Monomethyloidicyandiamide 2 g Cetylpyridinium bromide 0.l gPolyvinylpyrrolidone/vinylactate copolymer 0.5 g Acetic acid q.s.p. pH3.5 Water q.s.p. 100 g The hair is then wound up on curlers and set in aconventional manner. The resulting coifi'ure is long-lasting andattractive in appearance.

EXAMPLE C3 A solution having the following composition is applied tohair which has first been bleached and dyed:

Monomethyloldicyandiamide methyl ether 1 g Alcohol 10 cc Cetylpyridiniumbromide 0.15 g Phosphoric acid q.s.p. pH 2.5 Water q.s.p. 100 g Equallygood results with respect to springiness and long life of the wave areobtained.

EXAMPLE C5 A solution having the following composition is ap-Monomethyloldicyandiamide methyl ether 6 g Cetylpyridinium bromide O.l gVinyl acetate/polyvinylpyrrolidone copolymer 0.5 g Acetic acid q.s.p. pH3 Water q.s.p. 100 g The hair is set in a conventional manner. The hairbecomes hard and bright and the coiffure is fluffier than when given apermanent wave without treatment in accordance with the invention.

EXAMPLE C5 A solution having the following composition is applied as inExample C2 to hair which has previously been bleached:

Monomethyloldicyandiamide 3.5 g Cetyl trimethylammonium bromide 0.1 gAlcohol cc Acetic acid q.s.p. pH 3 Water q.s.p. 100 cc The resulting setis more stable than those imparted to hair which has not been treated inaccordance with the invention.

EXAMPLE C6 Hair which has first been bleached and rinsed is washed withan acid shampoo, and rinsed again. A gel having the followingcomposition is applied thereto:

Paraffin oil 23 g Oleic alcohol, 10 moles O.E. (sold under the tradenameBrij 96") 25 g Monomethyloldicyandiamide l g Perfume 0.2 g Water 52 gThe hair is then wound up on curlers and set in a conventional manner.After drying, the hair is easy to comb, bright, and springy.

EXAMPLE C7 A solution having the following composition is applied tobleached hair:

After having set the hair in a conventional manner, it is found that thetreated hair has a more attractive appearance and feel, and that theresulting coiffure is flufly and long lasting.

EXAMPLE C8 A solution having the following composition is applied underthe same conditions as in Example C7:

Monomethyloldicyandiamide ethyl ether 2 g Alcohol cc Perfume 0.1 gMonopotassium phosphate 0.3 g Water q.s.p. 100 cc Equally good resultsare obtained.

EXAMPLE C9 In order to produce an aerosol composition suitable for useas a setting lotion 50 grams of a 20 percent alcoholic solution preparedas described under Method I is prepared. A propellant gas is then added,which may be nitrogen at a pressure of 1.5 kg, or 2.7 g ofdichlorodifluoromethane, which is sold under the trade-name Freon 12.

A quantity of this aerosol composition sufficient to adequatelyimpregnate all its locks is sprayed onto hair which has first beenwashed, rinsed, and wound up on rollers. The hair is then dried under aheated hood and it is found that the set is springy and the hair isattractive, fluffy, and has an excellent feel.

The compositions set forth in Examples C1-C9 may be obtained by mixing aconcentrated alcoholic solution of the active compounds according to theinvention at the moment of use with an aqueous solution which suitablydilutes the concentrated aqueous solution.

The active compounds according to the invention may also be stored inthe form of a powder which is dissolved at the moment of use in theother components of the product.

In the case of the compositions according to this third embodiment ofthe invention and particularly in the case of those mentioned in theforegoing examples, there is no cumulative hardening of the hair sincethe condensation products of these methylol derivatives are easilyremoved by simply shampooing the hair.

It has also been found that those of the active compounds described inthe second embodiment of the invention in which R represents analkoxymethyl radical will produce satisfactory results even if not mixedwith a nitro derivative. The fourth form of the invention is accordinglycharacterized by the fact that it comprises at least one at leastpartially polymerizable compound capable of forming a bond by additionor condensation with the keratin of the hair and having at least onegroup of the formula:

R 1 I-CH 0 R in which:

R represents a hydrogen atom, a lower alkyl radical or an alkoxymethylradical, and

R represents a lower alkyl radical.

The nitrogen atom in the group is attached to a remainder which issufficiently electrophile to insure the chemical stability of the group.

In the present application the term lower alkyl radical is used to meanan alkyl radical having a number of carbon atoms small enough to renderthe alkoxymethyl compounds according to the invention sufficientlysoluble in the cosmetic carrier in which they are to be incorporated. Ingeneral, alkyl radicals having fewer than five carbon atoms will servethis purpose.

Among the sufficiently electrophile groups to which the nitrogen atommay be attached are those having a group, the carbon atom of which isdirectly attached to the nitrogen atom of the above formula.

The alkoxymethyl compounds according to the invention may be prepared byreacting the corresponding methylol compounds in a conventional mannerwith alcohols in the presence of an acid catalyst such as hydrochloricacid.

Methanol, ethanol, propano], isopropanol and butanol, for example, maybe employed.

According to the invention the compositions are preferably used in theform of hydroalcoholic solutions which, at the moment of use, contain aconcentration of active ingredients ranging from 0.2 to 10 percent andpreferably between 1 and 4 percent, by weight.

At the moment of use the compositions according to the invention mayhave an acid pH, between 2 and 5 for example, obtained by adding anorganic or mineral acid. These compositions may also be applied to thehair at a higher pH, when the acid catalyst is independently applied tothe hair either before or after the compositions according to theinvention.

Suitable acid catalysts include mineral acids such as phosphoric andsulfuric acid, acid salts such as monometallic phosphates, or evenorganic acids such as acetic, citric, and lactic acid.

The stability of these compositions is such that almost no release offormol occurs during their application, even when the hair is dried bythe application of heat.

In a preferred embodiment of the invention, the alkoxymethyl compoundsare kept in the form of a concentrated solution such as those listedabove, the concentration of the active ingredients being between and 30percent by weight.

Such concentrated alcoholic solutions are stable and may be stored.

At the moment of use, the addition of a given quantity of an aqueousliquid will produce the composition ready for use.

In accordance with the invention it is possible to use in thecomposition the same alcohol as that used to etherify the methylolcompound. However, the alkoxymethy] compound which has been prepared inpredetermined alcohol may be isolated and then redissolved in anotheralcohol if, for example, this alcohol has more valuable cosmeticproperties than the one used to produce the compound according to theinvention.

Of course, the compositions according to the invention may also containany ingredients customarily used in cosmetics, such as perfumes, dyes,penetrating agents, surface-active agents, etc.

The compositions according to the invention may take the form of aqueousor hydroalcoholic solutions, creams, emulsions or gels.

These compositions may also be packaged in the form of aerosols.

Among the active compounds according to the above Formula 1 which may beused in accordance with the invention, are the following, but this listis not allinclusive:

Bis methoxymethylurea, of the formula:

Methoxymethylurea, of the formula:

Ethoxymethylurea, of the formula:

- i.propyloxymethylurea, of the formula:

Trimethoxymethylmelamine, of the formula:

N rncornotmf w vnon ocni ,l N

NH-CH;OCH:

Ethyl dimethoxymethylcarbamate, of the formula:

CH OCH H C OOCN CH OOH;

Bismethoxymethyladipamide, of the formula:

Bis-butoxy-methylurea of the formula:

The fourth embodiment of the present invention also envisages a newprocess for strengthening hair which process is essentiallycharacterized by the fact that a composition as hereinbefore defined isapplied to the hair and that said hair is then heated to a temperaturebetween 25 and 45 C. This heat may be supplied while drying the hairwhich has first been impregnated with the composition according to theinvention.

In a first method of utilizing this fourth embodiment of the inventionthe acid catalyst is mixed into the composition containing the activecompounds.

In a second method of utilizing this fourth embodiment of the invention,the acid catalyst and the composition containing the active compoundsare applied separately, with the catalyst applied to the hair eitherbefore or after the composition according to the invention.

In order that this fourth embodiment of the invention may be betterunderstood, several methods of carrying it out will now be described,purely by way of illustration and example.

This lotion is applied to hair which has been strongly bleached. Then,after having wound the hair on setting rollers, it is dried by blowinghot air against it. After re- 21 moving the rollers and combining thehair, it is found that the hair is fluffier, softer, and brighter thanwhen set with a conventional lotion.

Moreover, the set lasts longer.

EXAMPLE D2 A composition having the following composition is prepared atthe moment of use:

Bismethoxymethylurea 0.2 g Trimethylcetylammonium bromide 0.1 g Waterq.s.p. 100 g Acetic acid q.s.p. pH 3.5

This lotion is applied to hair which has been treated with a mildbleach, and the hair is then wound up on setting rollers.

The hair is dried by applying hot air and after combing, the result is aset of good quality, the hair having recovered its original flufiinessand brightness.

EXAMPLE D3 A solution having the following composition is prepared:

Trimethoxymethylmelamine 30 g Ethanol 70 cc Water 20 cc EXAMPLE D4 0.5cc of normal hydrochloric acid is added to a suspension of 90 g ofmonomethylolurea in 180 cc of absolute methanol. The mixture is thenheated to reflux and under agitation for 15 minutes.

It is then neutralized, while hot, with sodium carbonate, cooled andfiltered. The filtrate is evaporated under vacuum at a temperature below40-45 C. The result is thick syrup which is highly soluble in water andin alcohol. An ethanol solution containing about 20 percent ofmethoxymethylurea is prepared and diluted at the moment of use with anaqueous solution of phosphoric acid having a pH value of 3, so as toreduce the concentration of the active compound to 4 percent. Thissolution is applied to hair which has been strongly bleached in the samemanner as a conventional setting lotion. The hair thus treated isspringy and bright, and the resulting set lasts longer than aconventional set EXAMPLE D 0.5 cc of normal hydrochloric acid is addedto a suspension of 90 g of monomethylolurea in 400 cc of absoluteethanol and the mixture is then heated to reflux under agitation forminutes. It is neutralized while hot with sodium carbonate, permitted tocool, and filtered.

A setting lotion is prepared at the moment of use by adding thefollowing solution to the concentrated alcoholic solution ofethoxymethylurea:

Polyvinylpyrrolidone/vinyl acetate copolymer 0.5 gTrimethylcetylammonium bromide 0.1 g Perfume 0.1 g acetic acid 10 ccWater q.s.p. 100 cc This brings the concentration of the resultingsolution to 8 percent in terms of ethoxymethylurea. This solution isapplied to hair which has been permanently waved and the hair is thenset in a conventional manner. Excellent results with respect to thequality, appearance and fluffiness of the hair are obtained.

EXAMPLE D6 Hair which has previously been bleached is carefully washedand dried and a detergent solution of citric acid at a pH of 3.5 isapplied. The hair is then impregnated with a solution having thefollowing composition:

Bismethoxymethylurea 3 g Trimethylcetylammonium bromide 0. gPolyvinylpyrrolidone/vinyl acetate copolymer 0.5g Perfume 0.] g Alcohol25 cc Water q.s.p. 100 u:

The hair is then wound up on curlers, again saturated with this solutionand dried under a hood for to minutes at about C. The hair is then foundto be springy and the set is long lasting.

EXAMPLE D7 A setting lotion having the following composition is appliedto hair which has first been bleached and dyed,

under the same conditions as in Example D2:

Ethyl dimethoxymethylcarbamate 2 g Polyvinylpyn'olidone/vinyl acetatecopolymer 2 g Perfume 0.l g Acetic acid q.s.p. pH 2.5 Water q.s.p. 10 ccThe hair is dried by applying hot air thereto while it is still wound upon the curlers, and a set having excellent holding power results.

EXAMPLE D8 Hair which has been washed and dried is impregnated with a 2percent lactic acid solution. A cream having the following compositionis then applied:

Lanette A.0. wax 4 g Oleic alcohol 4 g Trimethylcetylammonium bromide 2g Bis-methoxymethyladipamide l g Water 89 g The hair is then wound up oncurlers and dried under a hood for about 30 minutes at 45 C. The resultis a springy, long-lasting set.

The fifth form of our invention results from the suprising discoverythat while dimethylolurea and dimethylolthiourea have the disadvantageshereinbefore set forth with respect to the release of free formol andsolubility, monomethylolurea and monomethylolthiourea do not.

Specifically these particular monomethylols release from 2 to 3 timesless free formol than the corresponding dimethylols, and are at least 4or 5 times as soluble in water. Moreover, when in powder form, thesemonomethylols dissolve about 10 times as rapidly in water as thecorresponding dimethylols. On the other hand both monomethylolurea andmonomethylolthiourea compositions have the same characteristic ofimproving the quality of degraded hair possessed by the active compounds described in connection with the first four embodiments of thisinvention. In particular, when applied in conjunction with dyes, thesecompositions cause the dye to color the hair uniformly, even thoughpreviously bleached.

The fifth form of our invention accordingly relates to a cosmeticcomposition for improving the quality of degraded hair, said compositionbeing essentially characterized by the fact that it comprises insolution in a cosmetic recipient at least one active compound selectedfrom the group consisting of monomethylolurea and monomethylolthiourea.

These compositions may advantageously contain from 0.2 to 10 percent andpreferably from 2 to 5 percent by weight of the active compound. Theymay take the form of aqueous or hydro-alcoholic solutions, emulsions,creams, gels, or aerosols, and may include any of the additives such asperfumes, surface active agents, etc. conventionally used in cosmeticsThese compositions may also contain an acid polymerization catalystconsisting, for example, of a mineral acid such as phosphoric orsulfuric acid, or any of the organic acies or acid salts hereinbeforementioned. The acid catalyst should be introduced in an amountsufficient to bring the pH value of the composition to between about 1.5and 5.

The fifth form of our invention also relates to a method of improvingthe cosmetic properties of hair which comprises the step of applyingthereto a composition such as has just been described, and then heatingthe hair for 20 to 40 minutes at a temperature of from 35 to 50 C. Thisheating may advantageously take place during drying.

The acid catalyst may form part of the composition according to theinvention or be applied separately either before or after saidcomposition.

The invention makes it possible to bleach and permanently wave hair inrapid succession, or to permanently wave it twice in a relatively shortperiod of time, without damaging the hair.

Several examples showing how the invention may be carried out will nowbe described, purely by way of illustration:

EXAMPLE E1 The hair is completely bleached in a conventional manner, anda solution having the following composition is then applied for 30minutes at a temperature of 45 C:

Monomethylolurea 3.5 g Cetylpyridiniurn bromide 0.] g 20% acetic acid ccWater q.s.p. 100 cc The pH of this solution is about 3.

The hair is then dyed and dried in a conventional manner. The colortakes well, and the springiness and brightness of the hair areincreased, a result which is not found in the case of bleached hairwhich has not been treated in accordance with the invention beforedyeing.

EXAMPLE E2 Under the same conditions as in Example El, a solution havingthe following composition is applied to bleached hair:

Monomethylolthiourea 1.5 g 10% phosphoric acid 5 ccPolyvinylpyrrolidone/vinyl acetate copolymer 0.5 g Water q.s.p. cc

The pH of this solution is about 1.6.

The hair is then set in a conventional manner and dried under a hood at45-50 C. It is found that the hair treated in this way has an agreeablefeel," is quite springy, and is easy to comb.

EXAMPLE E3 Hair which has been previously bleached is shampooed with anacid cationic shampoo, rinsed, and dried. it is then saturated with asolution having the following composition:

Monomethylolurea 3 g compound having the formula:

( ll CON(CII )i-N 0.2 R.

ltNll(3lIC()ONu C2115 It =Copm) Water q.s.p. 100 cc The hair is thendried for 35 minutes at about 45 C.

l. is then permanently waved in a conventional manner and the moistenedhair is strong and of good quality. After being set in a conventionalmanner the hair is springy, fluffy and shiny, and holds the set wellover a period of time.

EXAMPLE E4 A solution having the following composition is applied tohair which has first been permanently waved:

Monomethylolthiourea 4 g 10% phosphoric acid 4 cc Ext. violet DC. No. 2(Cl violet No. 43) 0.005 g Ethyl alcohol 25 cc Water q.s.p. I00 cc ThepH of this solution is about 1.8.

The hair is dried in a conventional manner and excellent results withrespect to springiness and brightness are obtained.

EXAMPLE E5 EXAMPLE E6 A lotion consisting of a solution having thefollowing composition is applied to the hair:

Monomethylolurea 6 g Monomethylolthiourea 3 g Trimethylcetylammoniumbromide 0.1 g Water 90 cc The hair is then wound up on setting rollersand impregnated with a 20 percent lactic acid solution. It is driedunder a hood and the resulting set is springy and long lasting. The hairis substantially stiffened.

EXAMPLE E7 A solution having the following composition is applied tohair which has first been bleached and washed:

Monomethylolurea 10 g Phosphoric acid q.s.p. pH 2.5 Water q.s.p. 100 ccThe hair is left under a hood for about 10 minutes, remoistened, andpermanently waved in a conventional manner.

The hair is then in excellent condition all the way to its tips, and thelife of the permanent wave is substantially increased.

We claim:

1. A method for treating degraded hair to improve the strength andappearance thereof comprising applying to said hair in amounts effectiveto improve the strength and appearance thereof a cosmetic compositioncomprising a solution in a solvent selected from the group consisting ofwater and aqueous ethyl alcohol solution of a methylol compound of theformula R-lf-CHzOH wherein R is selected from the group consisting ofhydrogen and -H,o-Nc 000,115

wherein R" is selected from the group consisting of i.

- wherein is tQl h q R and ethr tm id v lent radical selected from thegroup consisting of b. -CH -CH -NH-CO; c. -CH -CH -NH-CS and (1.

,. H29 W v said compound being present in amounts of about 0.1-10percent by weight of said composition, polymerizing said methylolcompound on said hair by applying thereto an acidic catalyst in amountssufficient to cause polymerization of said methylol compound, saidcatalyst being selected from the group consisting of phosphoric acid,acetic acid, lactic acid, sulfuric acid, citric acid and monosodiumphosphate, and drying said hair.

2. The method of claim 1 wherein said acidic catalyst is appliedsimultaneously with said methylol compound.

3. The method of claim 1 wherein said acid catalyst is applied beforeapplication of said methylol compound.

4. The method of claim 1 wherein said acid catalyst is appliedsubsequent to the application of said methylol compound.

5. A method for treating degraded hair to improve the strength andappearance thereof comprising applying to said. hair in amountseffective to improve the strength and appearance thereof a cosmeticcomposition comprising a solution in a solvent selected from the groupconsisting of water and aqueous ethyl alcohol solution of a methylolcompound selected from the group consisting of monomethylol ethylcarbamate, dimethylol methylene ethyl bis-carbamate, dimethylolsuccinamide, monomethylol guanidine carbonate, N- methylol paratoluenesulfamide, dimethylol adipamide,N,N-dimethylol-(2-methyl-2-propyl)-propylene biscarbamate, monomethyloldimethyl hydantoin, monomethylol ethyleneurea, monomethylol ethylenethiourea and dimethylol ethylene thiourea, said compound being presentin amounts of about 0.1-10 percent by weight of said composition,polymerizing said methylol compound on said hair by applying thereto anacidic catalyst in amounts sufficient to cause polymerization of saidmethylol compound, said catalyst being selected from the groupconsisting of phosphoric acid, acetic acid, lactic acid, sulfuric acid,citric acid and monosodium phosphate and drying said hair.

6. A method for treating degraded hair to improve the strength andappearance thereof comprising applying to said hair in amounts effectiveto improve the strength and appearance thereof a cosmetic compositioncomprising a solution in a solvent selected from the group consisting ofwater and aqueous ethyl alcohol solution of a mixture of (a) a methylolcompound se lected from the group consisting of monomethyloldimethylhydantoin, monomethylol ethylene urea, dimethylol ethylenethiourea, monomethylol ethyl carbamate, dimethylol ethylene ethylbis-carbamate, dimethylol succinamide, monomethylolethylene thiourea,dimethylolthiourea, dimethylolurea, monomethylolurea,monomethylolthiourea, trimethylol melamine, monomethyloldicyandiamide,bismethoxymethylurea, monomethylol guanidine, N,N'-dimethylol-(2-methyl,2-propyl) propylene bis-carbamate, dimethylol adipamide,N,N-diethyl-N-methylolurea, N,N- dimethylol ethyleneurea, dimethylolethyl carbamate and tetramethylol acetylenediurea and (b) a nitrogenderivative selected from the group consisting of urea, melamine,dicyandiamide, N,N-diethylurea, ethyleneurea, isopropyl carbamate,dimethyl hydantoin, ethylene thiourea, guanidine carbonate andsuccinamide, said methylol compound being present in amounts of 05-12percent by weight of said composition, said nitrogen derivative beingpresent in amounts such that the number of NH groups supplied by saidnitrogen derivative is between 0. ll .0 times the number of methylolgroups supplied by said methylol compound, polymerizing said methylolcompound on said hair by applying thereto an acidic catalyst in amountssufficient to cause polymerization of said methylol compound, saidcatalyst being selected from the group consisting of phosphoric acid,acetic acid, lactic acid, sulfuric acid, citric acid and sodium acidphosphate, and drying said hair.

7. The method of claim 6 wherein said acidic catalyst is appliedsimultaneously with said methylol compound.

8. The method of claim 6 wherein said acidic catalyst is applied beforeapplication of said methylol compound.

9. The method of claim 6 wherein said acidic catalyst is appliedsubsequent to the application of said methylol compound.

10. A cosmetic composition for treating degraded hair to improve thestrength and appearance thereof, said composition comprising a solutionin a solvent selected from the gorup consisting of water and aqueousethyl alcohol solution of a mixture of (a) a methylol compound selectedfrom the group consisting of monomethylol dimethylhydantoin,monomethylol ethylene urea, dimethylol ethylene thiourea, monomethylolethyl carbamate, dimethylol ethylene ethyl biscarbamate, dimethylolsuccinamide, monomethylolethylene thiourea, dimethylolthiourea, dimethylolurea, monomethylolurea, monomethylolthiourea, trimethylolmelamine, monomethyloldicyandiamide, bismethoxymethylurea, monomethylolguanidine, N,N- -dimethylol-(2-rnethyl,2-propyl)propylene biscarbamate,dimethylol adipamide, N,N-diethyl N- methylolurea, N,N-dimethylolethyleneurea, dimethylol ethylcarbamate and tetramethylolacetylenediurea and (b) a nitrogen derivative selected from the groupconsisting of urea, melamine, dicyandiarnide, N,N diethylurea, ethyleneurea, isopropyl carbamate, dimethyl hydantoin, ethylene thiourea,guanidline carbonate and succinamide, said methylol compound beingpresent in amounts of 05-12 percent by weight of said composition andsaid nitrogen derivative being present in amounts such that the numberof NH groups supplied by said nitrogen derivative is between 0. ll .0times the number of methylol groups supplied by said methylol compound.

11. A method for treating degraded hair to improve the strength andappearance thereof comprising applying to said hair in amounts effectiveto improve the strength and appearance thereof a cosmetic ompositioncomprising a solution in a solvent selected from the group consisting ofwater and aqueous ethyl alcohol solution of a compound of the formulawherein R is selected from the group consisting of hydrogen, methyl andethyl, said compound being present in amounts of 02-10 percent by weightof said composition, polymerizing said compound on said hair by applyingthereto an acidic catalyst in amounts sufficient to cause polymerizationof said compound, said catalyst being selected from the group consistingof acetic, lactic, citric, phosphoric and sulfuric acid andmonopotassium phosphate, and drying said hair.

12. The method of claim 11 wherein said acidic cata lyst is appliedsimultaneously with said methylol compound.

13. The method of claim 1 1 wherein said acidic catalyst is appliedbefore application of said methylol compound.

14. The method of claim 1 1 wherein said acidic catalyst is appliedsubsequent to the application of said methylol compound.

15. A pressurized sprayable aerosol composition for treating degradedhair to improve the strength and appearance thereof comprising anethanolic solution of a compound of the formula wherein R is selectedfrom the group consisting of hydrogen, methyl and ethyl, said compoundbeing present in amounts of 20 percent by weight of said solution and anaerosol propellant selected from the group consisting of nitrogen anddichlorodifluoromethane.

16. A method for treating degraded hair to improve the strength andappearance thereof comprising applying to said hair in amounts effectiveto improve the strength and appearance thereof a cosmetic compositioncomprising a solution in a solvent selected from the group consisting ofwater and aqueous ethyl alcohol solution of a compound selected from thegroup consisting of bis-methoxymethylurea, methoxymethylurea,ethoxymethylurea, isopropyloxymethylurea, trimethoxymethylmelamine,ethyl dimethoxymethylcarbamate, bismethoxymethyladipamide andbisbutoxy-methylurea, said composition containing 0.2l0 percent byweight of said compound, polymerizing said compound on said hair byapplying thereto an acidic catalyst in amounts sufficient to causepolymerization of said compound, said catalyst being selected from thegroup consisting of phosphoric, acetic, lactic, sulfuric and citric acidand drying said hair.

17. The method of claim 16 wherein said acidic catalyst is appliedsimultaneously with said compound.

18. The method of claim 16 wherein said acidic catalyst is appliedbefore application of said compound.

19. The method of claim 16 wherein said acidic catalyst is appliedsubsequent to the application of said compound.

20. A method for treating degraded hair to improve the strength andappearance thereof comprising applying to said hair in amounts effectiveto improve the strength and appearance thereof a cosmetic compositioncomprising a solution in a solvent selected from the group consisting ofwater and aqueous ethyl alcohol solution of a compound selected from thegroup consisting of monomethylolurea and monomethylolthb ourea, saidcompound being present in amounts of 0.2- percent by weight of saidcomposition, polymerizing said compound on said hair by applying theretoan acidic catalyst in amounts sufficient to cause polymerization of saidcompound, said catalyst being selected from the group consisting ofphosphoric, sulfuric, acetic, citric and lactic acid, and heating saidhair at a temperature between 3550 C for a period of about 204Ominutes.-

21. The method of claim 20 wherein said acidic catalyst is admixed withsaid composition, the pH of said composition ranging between 1.5-5.0.

22. The method of claim 20 wherein said acidic catalyst is appliedbefore application of said composition.

23. The method of claim 20 wherein said acidic catalyst is appliedsubsequent to the application of said composition and prior to heatingsaid hair.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. [772 OI,6 Dated mg h r 2Q 1913 Gregoire Kalopissis, Jean Louis Abegg, HenriInventor(s) d l d It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

In the Heading:

Name of third inventor should be changed from "Henry DeBeaulie" to--Henri deBeaulieu-.

Please add --C1a1ms priority, application Iuxembourg 5 ,9 3: p i 19,l966--,

Signed and sealed this 2nd day of July 1974.

(SEAL) Attest:

EDWARD M. FLETCHER,JR. C.MARSHALL DANN Attesting Officer Commissioner ofPatents M PO-1050 (10-69) USCOMM-DC 603764 69 u 5. aovnnuzuv "mums onlcinu o-su-u4

2. The method of claim 1 wherein said acidic catalyst is appliedsimultaneously with said methylol compound.
 3. The method of claim 1wherein said acid catalyst is applied before application of saidmethylol compound.
 4. The method of claim 1 wherein said acid catalystis applied subsequent to the application of said methylol compound.
 5. Amethod foR treating degraded hair to improve the strength and appearancethereof comprising applying to said hair in amounts effective to improvethe strength and appearance thereof a cosmetic composition comprising asolution in a solvent selected from the group consisting of water andaqueous ethyl alcohol solution of a methylol compound selected from thegroup consisting of monomethylol ethyl carbamate, dimethylol methyleneethyl bis-carbamate, dimethylol succinamide, monomethylol guanidinecarbonate, N-methylol paratoluene sulfamide, dimethylol adipamide,N,N''-dimethylol-(2-methyl-2-propyl)-propylene bis-carbamate,monomethylol dimethyl hydantoin, monomethylol ethyleneurea, monomethylolethylene thiourea and dimethylol ethylene thiourea, said compound beingpresent in amounts of about 0.1-10 percent by weight of saidcomposition, polymerizing said methylol compound on said hair byapplying thereto an acidic catalyst in amounts sufficient to causepolymerization of said methylol compound, said catalyst being selectedfrom the group consisting of phosphoric acid, acetic acid, lactic acid,sulfuric acid, citric acid and monosodium phosphate and drying saidhair.
 6. A method for treating degraded hair to improve the strength andappearance thereof comprising applying to said hair in amounts effectiveto improve the strength and appearance thereof a cosmetic compositioncomprising a solution in a solvent selected from the group consisting ofwater and aqueous ethyl alcohol solution of a mixture of (a) a methylolcompound selected from the group consisting of monomethyloldimethylhydantoin, monomethylol ethylene urea, dimethylol ethylenethiourea, monomethylol ethyl carbamate, dimethylol ethylene ethylbis-carbamate, dimethylol succinamide, monomethylolethylene thiourea,dimethylolthiourea, dimethylolurea, monomethylolurea,monomethylolthiourea, trimethylol melamine, monomethyloldicyandiamide,bismethoxymethylurea, monomethylol guanidine,N,N''-dimethylol-(2-methyl,2-propyl) propylene bis-carbamate, dimethyloladipamide, N,N-diethyl-N''-methylolurea, N, N-dimethylol ethyleneurea,dimethylol ethyl carbamate and tetramethylol acetylenediurea and (b) anitrogen derivative selected from the group consisting of urea,melamine, dicyandiamide, N,N-diethylurea, ethyleneurea, isopropylcarbamate, dimethyl hydantoin, ethylene thiourea, guanidine carbonateand succinamide, said methylol compound being present in amounts of0.5-12 percent by weight of said composition, said nitrogen derivativebeing present in amounts such that the number of NH2 groups supplied bysaid nitrogen derivative is between 0.1-1.0 times the number of methylolgroups supplied by said methylol compound, polymerizing said methylolcompound on said hair by applying thereto an acidic catalyst in amountssufficient to cause polymerization of said methylol compound, saidcatalyst being selected from the group consisting of phosphoric acid,acetic acid, lactic acid, sulfuric acid, citric acid and sodium acidphosphate, and drying said hair.
 7. The method of claim 6 wherein saidacidic catalyst is applied simultaneously with said methylol compound.8. The method of claim 6 wherein said acidic catalyst is applied beforeapplication of said methylol compound.
 9. The method of claim 6 whereinsaid acidic catalyst is applied subsequent to the application of saidmethylol compound.
 10. A cosmetic composition for treating degraded hairto improve the strength and appearance thereof, said compositioncomprising a solution in a solvent selected from the gorup consisting ofwater and aqueous ethyl alcohol solution of a mixture of (a) a methylolcompound selected from the group consisting of monomethyloldimethylhydantoin, monomethylol ethylene urea, dimethylol ethylenethiourea, monomethylol ethyl carbamate, dimethylol ethylene ethylbis-carbamate, dimethylol succinamide, monomethylolethylene thiourea,dimethylolthiourea, dimethylolurea, monometHylolurea,monomethylolthiourea, trimethylol melamine, monomethyloldicyandiamide,bismethoxymethylurea, monomethylol guanidine,N,N''-dimethylol-(2-methyl,2-propyl)propylene bis-carbamate, dimethyloladipamide, N, N-diethyl N''-methylolurea, N,N-dimethylol ethyleneurea,dimethylol ethylcarbamate and tetramethylol acetylenediurea and (b) anitrogen derivative selected from the group consisting of urea,melamine, dicyandiamide, N,N-diethylurea, ethylene urea, isopropylcarbamate, dimethyl hydantoin, ethylene thiourea, guanidine carbonateand succinamide, said methylol compound being present in amounts of0.5-12 percent by weight of said composition and said nitrogenderivative being present in amounts such that the number of NH2 groupssupplied by said nitrogen derivative is between 0.1-1.0 times the numberof methylol groups supplied by said methylol compound.
 11. A method fortreating degraded hair to improve the strength and appearance thereofcomprising applying to said hair in amounts effective to improve thestrength and appearance thereof a cosmetic omposition comprising asolution in a solvent selected from the group consisting of water andaqueous ethyl alcohol solution of a compound of the formula
 12. Themethod of claim 11 wherein said acidic catalyst is appliedsimultaneously with said methylol compound.
 13. The method of claim 11wherein said acidic catalyst is applied before application of saidmethylol compound.
 14. The method of claim 11 wherein said acidiccatalyst is applied subsequent to the application of said methylolcompound.
 15. A pressurized sprayable aerosol composition for treatingdegraded hair to improve the strength and appearance thereof comprisingan ethanolic solution of a compound of the formula
 16. A method fortreating degraded hair to improve the strength and appearance thereofcomprising applying to said hair in amounts effective to improve thestrength and appearance thereof a cosmetic composition comprising asolution in a solvent selected from the group consisting of water andaqueous ethyl alcohol solution of a compound selected from the groupconsisting of bis-methoxymethylurea, methoxymethylurea,ethoxymethylurea, isopropyloxymethylurea, trimethoxymethylmelamine,ethyl dimethoxymethylcarbamate, bismethoxymethyladipamide andbis-butoxy-methylurea, said composition containing 0.2-10 percent byweight of said compound, polymerizing said compound on said hair byapplying thereto an acidic catalyst in amounts sufficient to causepolymerization of said compound, said catalyst being selected from thegroup consisting of phosphoric, acetic, lactic, sulfuric and citric acidand drying said hair.
 17. The method of claim 16 wherein said acidiccatalyst is applied simultaneously with said compound.
 18. The method ofclaim 16 wherein said acidic catalyst is applied before application ofsaid compound.
 19. The method of claim 16 wherein said acidic catalystis applied subsequent to the application of said compound.
 20. A methodfor treating degraded hair to improve the strength and appearancethereof comprising applying to said hair in amounts effective to improvethe strength and appearance thereof a cosmetic composition comprising asolution in a solvent selected from the group consisting of water andaqueous ethyl alcohol solution of a compound selected from the groupconsisting of monomethylolurea and monomethylolthiourea, said compoundbeing present in amounts of 0.2-10 percent by weight of saidcomposition, polymerizing said compound on said hair by applying theretoan acidic catalyst in amounts sufficient to cause polymerization of saidcompound, said catalyst being selected from the group consisting ofphosphoric, sulfuric, acetic, citric and lactic acid, and heating saidhair at a temperature between 35*-50* C for a period of about 20-40minutes.
 21. The method of claim 20 wherein said acidic catalyst isadmixed with said composition, the pH of said composition rangingbetween 1.5-5.0.
 22. The method of claim 20 wherein said acidic catalystis applied before application of said composition.
 23. The method ofclaim 20 wherein said acidic catalyst is applied subsequent to theapplication of said composition and prior to heating said hair.